JP6175577B2 - Gas sensor element - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is filed on May 28, 2014 and January 26, 2015, respectively, and is hereby incorporated by reference in its entirety. US Provisional Patent Applications 62 / 003,753 and 62 / Claims 107,961 priority.

  Some embodiments relate to medical devices and also to oxide compositions for qualitative or quantitative analysis of exhaled components.

  Scientists have discovered a link between a physical condition associated with the presence of certain gases in the exhaled mammal and certain diseases. For that purpose, gas detection devices have been reported. However, some acetone detectors require operating temperatures above ambient, in some cases exceeding 300 ° C. Heating provides energy to the semiconductor material and can increase the movement of electrons across the band gap. However, such high operating temperatures can contribute to difficulties in creating portable devices.

  Therefore, there is a need for an acetone sensor that operates at room temperature for use in portable devices that can be used for diagnosis and self-monitoring of outpatients with various physical conditions including diabetes.

  The present application relates to an acetone sensor element that detects the presence of acetone in a gas sample, eg, exhaled breath. Some embodiments relate to gas sensor elements such as acetone sensor elements or ethanol sensor elements that operate at ambient temperature.

  Some embodiments include a first electrode and a second electrode that are separated by a gap of about 1 to about 10 mils, and a polycrystal that is in physical contact with both the first electrode and the second electrode. And a gas sensor element including a conductive n-type semiconductor material.

  Some embodiments include a method for identifying acetone in a subject's breath, comprising exposing a mammalian breath sample to a gas sensor comprising the gas sensor element of claim 1, wherein the presence of acetone is a sensor. Detected by changes in resistivity.

Some embodiments
P _1-x B (Formula 1)
Including a semiconductor composite having a sensor element comprising:
P is an n-type semiconductor material, B is boron, and x is ≦ 0.10. In some embodiments, x is> 0.0001. In some embodiments, the n-type semiconductor material can be tungsten oxide (WO ₃ ). In some embodiments, WO ₃ is epsilon phase WO ₃ (ε-WO ₃ ). In some embodiments, the sensor element can further include a cocatalyst. In some embodiments, the cocatalyst can be a noble metal. In some embodiments, the noble metal is palladium, gold, or platinum. In some embodiments, the cocatalyst can be a transition metal oxide. In some embodiments, the transition metal oxide can be an oxide of Co, Mn, Ni, or Cu.

In some embodiments, a gas sensor element is provided. The sensor element can comprise a physical mixture of WO ₃ and CeO ₂ . In some embodiments, the physical mixture has a 1: 1 molar ratio. In some embodiments, WO ₃ is gamma phase WO ₃ . In some embodiments, WO ₃ is an epsilon phase. In some embodiments, the sensor element can further include a cocatalyst. In some embodiments, the cocatalyst can be selected from metal oxides. In some embodiments, the metal oxide is CeO ₂ or TiO ₂ .

  In some embodiments, a method for making a sensor composition is described that includes creating an aqueous n-type semiconductor precursor solution, heating the solution in a preheated device, and the preheated device. Includes preheating to substantially close to the combustion temperature of the aqueous solution, subjecting the precursor solution to a combustion reaction, and annealing the combustion reaction product. In some embodiments, the equipment can be preheated to at least about 420 degrees Celsius.

In some embodiments, a method is described, the method comprising combustion synthesizing boron-doped epsilon or gamma phase WO ₃ semiconductor and first and second spaced apart electrodes interdigitated. And providing a combustion synthesized boron-doped epsilon or gamma phase semiconductor between the first and second spaced apart electrodes. In some embodiments, the method further includes increasing the specific surface area (SSA) of the synthesized boron doped epsilon or gamma phase semiconductor to greater than 10 m ² / g, boron doped epsilon or gamma phase WO _3. Ball milling the semiconductor for about 5 to about 48 hours. In some embodiments, increasing the boron doped epsilon or gamma phase WO ₃ semiconductor SSA involves ball milling between boron doped epsilon or gamma phase WO ₃ semiconductor from about 5 to about 25 hours . In some embodiments, increasing the SSA includes sonicating a boron-doped epsilon or gamma phase WO ₃ semiconductor prior to placement between the first and second electrodes. In some embodiments, the method can further include adding a metal oxide to the boron-doped epsilon or gamma phase WO ₃ semiconductor.

  These and other embodiments are described in more detail below.

FIG. 1 is a plan view of several embodiments of the apparatus described herein. FIG. 2 is an elevational view of an embodiment of the apparatus described herein. FIG. 3 is an elevation view of an embodiment of the apparatus described herein. FIG. 4A is a schematic diagram of several embodiments of the apparatus described herein. FIG. 4B is a schematic diagram of some embodiments of the apparatus described herein. FIG. 5 illustrates an X-ray diffraction pattern of an embodiment of the n-type material described herein. FIG. 6 is a scanning electron microscope image of a surface containing a composite element as described herein. FIG. 7 is a schematic view of an inspection instrument used in this specification. FIG. 7A is an illustration of an embodiment of the apparatus described herein. FIG. 8 is a graph illustrating the resistivity response for a 100 ppm acetone sample of the sensor embodiment described in Example 14. FIG. 9 is a graph illustrating the response of the resistivity for the 1 ppm acetone sample of the sensor embodiment described in Example 13. FIG. 10 is a graph illustrating the resistivity response for the 1 ppm acetone sample of the sensor embodiment described in Example 15. FIG. 11 is a graph illustrating the response of resistivity to different concentrations of an acetone sample for the sensor embodiment described in Example 15. FIG. 12A is a scanning electron microscope image of particles synthesized by combustion as described in Example 1. FIG. 12B is a scanning electron microscopic image of particles synthesized by combustion as described in Example 11. FIG. 13 is a graph illustrating the diameter population of n-type semiconductor material used in the sensor embodiment described in Example 14. FIG. 14 is a graph illustrating the diameter population of n-type semiconductor material used in the sensor embodiment described in Example 14. FIG. 15 is a graph illustrating the resistivity response of the sensor embodiment described in Example 18A to a 1 ppm acetone sample, 0.65 ppm ethanol, and 0.66 ppm isoprene.

  The term “polycrystalline material” encompasses any material that includes a plurality of grains (ie, crystals) of materials joined together directly by intergranular bonding. The crystal structure of the individual crystal grains of the material may be spatially randomly oriented in the polycrystalline material.

  The term “intergranular bond” as used herein encompasses any direct atomic bond (eg, covalent, metallic, etc.) between atoms in adjacent grains of the material.

  The term “epsilon phase” as used herein has its usual meaning known to those skilled in the art.

  The term “gamma phase” as used herein has the usual meaning known to those skilled in the art.

  As used herein, the term “doped” refers to an element that is incorporated into the crystal lattice of a compound, eg, substituted at a defined position in the crystal lattice or otherwise included in the crystal between the lattice. Include.

  The term “supported” encompasses a non-valent combination of a first material, eg, an n-type semiconductor material and a second material, eg, a physical mixture and / or adjacent arrangement, eg, Pt, Ag , Pd, Au and other precious metals are on the surface.

  The term “n-type semiconductor” has its ordinary meaning known to those skilled in the art.

  The term “room temperature” has the usual meaning known to the person skilled in the art.

Some embodiments have the formula 1
P _1-x B (Formula 1)
And with respect to Formula 1, P can be an n-type semiconductor material, B can be boron, and x is ≦ 0.10. In some embodiments, x is from a lower limit of 0.0001, 0.01, 0.05, 0.10 wt% to an upper limit of about 0.4, 0.5%, 0.75, 1.0 wt%. And / or between any combination of the stated limits. In some embodiments, x may be 0.225 g (B) / 100 g (semiconductor).

Tungsten oxide is one material used for gas sensors. Tungsten oxide (WO ₃ ) crystals can be formed by the corner and ridge sharing of the WO ₆ octahedron. Various phases such as monoclinic II (epsilon [ε] phase), triclinic (delta [δ] phase), monoclinic I (gamma [γ] phase), tetragonal (beta [β] phase), Tetragonal (alpha [α] phase) and cubic WO ₃ are obtained by angle sharing. Monoclinic phase II can only be stable at sub-zero temperatures, and monoclinic phase I can be the most stable phase at room temperature. ε-phase tungsten oxide may be useful for gas sensors.

In some embodiments, the n-type semiconductor material can be polycrystalline. In some embodiments, n-type semiconductor material can be a WO _3. In some embodiments, the n-type semiconductor has an absorption edge of at least 600 nm, at least 550 nm, at least 500 nm, at least 475 nm, and / or at least 450 nm. In some embodiments, the n-type semiconductor material can have an octahedral lattice. In some embodiments, the n-type semiconductor material can be a monoclinic phase material. In some embodiments, the n-type semiconductor material can be a monoclinic I-phase material. In some embodiments, the n-type semiconductor material can be a monoclinic phase II material. In some embodiments, the n-type semiconductor material can have a spontaneous dipole moment. In some embodiments, WO ₃ can be epsilon phase WO ₃ (ε-WO ₃ ). In some embodiments, WO ₃ may be gamma phase WO ₃ (γ-WO ₃ ). In some embodiments, the n-type semiconductor can be epsilon phase tungsten oxide, gamma phase tungsten oxide, and / or mixtures thereof. Comparison of the X-ray diffraction patterns of a given standard and product sample is one of several methods that can be used to determine whether a sample contains a particular phase. Exemplary standards include the National Institute of Standards and Technology (NIST) (Gaithersburg, MD, USA) and / or the International Diffraction Data Center (ICDD, formerly the Joint Committee on Powder Diffraction Standards [JCPDS]) (Newtown (Square, PA, USA).

In some embodiments, the semiconductor can include at least ε-WO ₃ and at least a second n-type semiconductor material. In some embodiments, ε-WO ₃ comprises at least 55%, at least 60%, at least 65%, at least 70%, 90%, 95%, or 99% of the n-type semiconductor material. In some embodiments, the% of ε-WO ₃ is% by weight. In some embodiments, the% of ε-WO ₃ is mol%. In some embodiments, the ratio of ε phase WO ₃ to γ phase is expressed as an XRD peak of ε phase WO ₃ at about 49.34 two theta to an XRD peak of γ phase WO ₃ at about 26.44 two theta. Can be done. While not intending to be bound by theory, the e-WO ₃ spontaneous dipole can be associated with the lattice of the material, so that changes in the lattice can change the strength of the dipole (in other words, the spontaneous polarization of Change). It is believed that changes in the spontaneous dipole moment can lead to changes in the surface charge of the material.

WO ₃ compounds, such as nanopowder, have many, including thermal plasma (direct current, including radio frequency fusion coupled plasma (RF-ICP)), solvothermal, solid state reaction, pyrolysis (flame spray), and combustion It can be prepared by different methods. In some embodiments, the WO ₃ compound can be combustion synthesized. The combustion synthesis method described in PCT application PCT / US2013 / 10201 filed January 4, 2014, which is incorporated herein by reference in its entirety, is useful. This is because high temperatures can help dope boron into the WO ₃ lattice and / or contribute to stabilization of the ε-phase WO ₃ . Hence, a combustion doping process may be preferred. For example, when preparing WO ₃ nanopowder, additional additives in water, such as ammonium metatungstate, ammonium nitrate, and / or a dispersion of glycine (5-20 wt% solids in water) are used with a two-fluid atomizer. Can be sprayed into the plasma volume. Preferably, the precursor may be present up to about 20 wt% solids in water. The plasma can be operated by, for example, argon, nitrogen, and / or oxygen gas at about 25 kW plate voltage. The particles formed from the condensed vapor from the plasma can then be collected on the filter. In some embodiments, the surface area of the particles measured using BET is from about 1 m ² / g to about 500 m ² / g, from about 15 m ² / g to 30 m ² / g, or up to about 20 m ² / g. It is a range. In some embodiments, the resulting WO ₃ can be heated to about 200 ° C. to about 700 ° C. or about 300 ° C. to about 500 ° C.

In some embodiments, the dipole moment of an n-type semiconductor can be modified by changing the semiconductor crystal lattice. In some embodiments, the crystal lattice is modified by doping the semiconductor. In some embodiments, the n-type semiconductor can be doped with at least one naturally occurring element, eg, a group III acceptor element such as B, with a noble gas element. In some embodiments, the group III acceptor element can be B. In some embodiments, the dopant can be B. In some embodiments, the dopant can be B ³⁺ .

In some embodiments, the polycrystalline n-type semiconductor material comprises an epsilon phase WO ₃ doped with boron, such as B, B ⁺ , B ²⁺ , or B ³⁺ .

As described above, in some embodiments, the dopant concentration, eg, the proportion of B, B ⁺ , B ²⁺ , or B ³⁺ is about 0.0001% by weight of the n-type semiconductor, about 0.0. From the lower limit of 01%, about 0.01%, 0.05%, 0.08%, or 0.10% to about 0.15%, about 0.2%, about 0.4%, about 0.0. It may be between an upper limit of 5%, about 0.75%, about 1%, about 2%, or about 5% and / or any combination of the stated limits. In some embodiments, X can be about 0.225 g (B) / 100 g (semiconductor). Without wishing to be limited by theory, if the x and / or dopant concentration is above the threshold amount, the amount of epsilon phase WO ₃ and / or boron present will provide the desired room temperature phase stability. It may be insufficient to provide. In addition, without intending to be limited by theory, also when the concentration of x and / or dopant is below a threshold amount, the amount of ε-WO ₃ and / or boron present is as desired. It is believed that it may be insufficient to provide room temperature phase stability. Without wishing to be limited by theory, it is believed that if the concentration of x and / or dopant is below a threshold amount, the dopant may segregate instead of doping into the lattice.

Doped elements can generally be provided as precursors added during synthesis. In some embodiments, the dopant may have an ionic diameter that is small enough to increase the stability of the ε-phase WO ₃ . In some embodiments, the dopant may have an ionic diameter of less than about 50 pm (1 × 10 ⁻¹² meters). In some embodiments, the dopant can have an ionic diameter from about 5 pm, 10 pm, 15 pm, 20 pm, 30 pm, 35 pm, up to about 45 pm, up to about 50 pm, up to about 55 pm. Exemplary ionic diameters of ionic species, typically at 90% semiconductor and 10% dopant, are listed in Table 1.

The ionic diameter of the desired ionic species can be specified according to Equation 2.
([% Molar amount of semiconductor × semiconductor ion size] + molar amount of dopant × dopant ion size) / [90% + 10%] 100 (Formula 2)

For example, to specify the B ion size, 90 × [W ⁶⁺ ion size] [6660] +. 10 × [[580] / 100, resulting in a calculated B ³⁺ ion size of about 41 pm. In some embodiments, the dopant can be boron. In some embodiments, the dopant can be B ³⁺ , eg, having an ionic diameter of about 41 pm. Without wishing to be bound by theory, doping with dopant molecules having an ionic diameter smaller than the ε-phase WO ₃ , eg, about 74 pm, can shrink the overall unit cell volume of the crystal, and ε-WO ₃ at room temperature. It is thought to contribute to the stability of

  In some embodiments, the n-type semiconductor can carry at least one metal. Supported elements include impregnation (Liu, M. et al., Chemistry of Materials, published online 2011), photoreduction (Abe et al., Journal of the American Chemical Society, 130: 7780-7781, 2008), and It can be provided by a post synthesis method such as sputtering. In some embodiments, the loading can be performed by electrostatic adsorption. As a preferred embodiment, loading a metal on a semiconductor can be performed as described in US Patent Publication No. US2008 / 0241542, which is incorporated herein by reference in its entirety.

In some embodiments, the supported element is a noble metal element. In some embodiments, the supported elements can be noble metal elements, noble metal element oxides, noble metal element peroxides (Ag ₂ O ₂ ), and / or noble metal element hydroxides. In some embodiments, the noble metal element (s) can be Au, Ag, Pt, Pd, Ir, Ru, Rh, or oxides and / or hydroxides thereof. In some embodiments, the supported elements are selected from transition metals, their oxides, and / or hydroxides. In some embodiments, the supported element can be Pt or its oxides and hydroxides. In some embodiments, the supported elements can be selected from different groups of elements including at least one transition metal and at least one noble metal, or their respective oxides and hydroxides.

Cocatalysts include materials that improve sensor sensitivity. In some embodiments, the cocatalyst may improve sensor sensitivity. For example, the cocatalyst can increase sensitivity by at least about 1.2, at least about 1.5, at least about 1.8, at least about 2, at least about 3, or at least about 5. One method of quantifying the sensitivity ratio may include comparing the determined sensitivity value of a sensor that includes a cocatalyst with that of a sensor that does not include a cocatalyst. For example, a suitable method for determining the sensitivity value is by the formula R _air / R _gas or R _gas / R _air , where R _air is the measured resistivity (ohms) of air and R _gas is the analyte The measured resistivity of a gas such as acetone. See Table 2.

  For example, the presence of a cocatalyst can increase the sensitivity of the sensor by about 80% over its original sensitivity. In some embodiments, the increase in sensitivity is about 10%, about 17.5%, greater than about 25%, such as about 35-50% and / or about 50 to about 90%, such as about 80% of its original sensitivity. %.

  Some cocatalysts can be compounds or semiconductors capable of being reduced by electron transfer from the semiconductor conduction band. For example, the cocatalyst may have a conduction band having an energy lower than that of the semiconductor, or the cocatalyst may have the lowest unoccupied molecular orbital having an energy lower than that of the semiconductor. An electron loses energy when it moves into a “lower energy” band or molecular orbital. An electron gains energy when it moves into a “higher energy” band or molecular orbital.

Without intending to be limited by theory, the inventor believes that some cocatalysts can be metal oxides capable of reducing O ₂ . For example, CeO ₂ can reduce O ₂ gas by electron transfer. In doing so, it is believed that Ce ³⁺ moves electrons to O ₂ and is consequently converted to Ce ⁴⁺ . In a semiconductor composition, the semiconductor can transfer electrons to CeO ₂ , thus converting Ce ⁴⁺ to Ce ³⁺ , and then Ce ³⁺ can reduce O ₂ . Ce ³⁺ can also be present as a result of an equilibrium process involving CeO ₂ and O ₂ and the superoxide radical ion O ²⁻ . O ₂ and superoxide radical ions can be adsorbed on the surface of solid CeO ₂ in such an equilibrium process or present in the atmosphere. Ce ³⁺ may also be present as a result of oxidation and reduction reactions with cerium species of different oxidation states that may be intentionally added or present as impurities.

Some cocatalysts may be capable of converting O ₂ into superoxide radical ions in the atmosphere. For example, CeO ₂ has the ability to convert oxygen in the atmosphere into superoxide radical ions. Some equilibration and / or electron transfer processes described above are believed to be contributing to this characteristic of CeO _2. Such conversion can occur under a variety of conditions, such as ambient conditions, such as normal atmospheric oxygen concentrations, such as a molar concentration of about 10% to about 30%, about 15% to about 25%, or about 20% oxygen, Ambient temperature such as about 0 ° C to about 1000 ° C, about 0 ° C to about 100 ° C, about 10 ° C to about 50 ° C, or about 20 ° C to about 30 ° C, and about 0.5 to about 2 atm, about 0.8 atm From about 1.2 atm, or about 1 atm. Such conversion can also occur under elevated or reduced temperatures, pressures, or oxygen concentrations.

Some cocatalysts may have a higher energy valence band or highest occupied molecular orbital than the semiconductor valence band. This may allow holes in the semiconductor valence band to migrate to the highest occupied molecular orbital or valence band of the cocatalyst. Then, holes in the valence band or the highest occupied molecular orbital of the co-catalyst is H _{2 O} or OH ^- may in OH ^· to oxidize. For example, if WO ₃ is chosen as the semiconductor, examples of such cocatalysts can include anatase TiO ₂ , SrTiO ₃ , KTaO ₃ , SiC, and / or KNbO ₃ .

In some embodiments, the cocatalyst can be inorganic. In some embodiments, the inorganic cocatalyst can be a binder. In some embodiments, the cocatalyst can be an oxide such as a metal dioxide, including CeO ₂ , TiO ₂ , or the like. In some embodiments, the _co-catalyst may be a _{SiO 2, SnO 2, Al 2} O 3, ZrO 2, Fe 2 O 3, Fe 3 O 4, NiO, Nb 2 O 5, and / or CeO _2. In some embodiments, the composite material may include a physical mixture of an inorganic cocatalyst and a semiconductor material. In another embodiment, the semiconductor material to a co-catalyst, for example, CeO ₂ ratio is 40 to 60 mole% of the semiconductor material and from 60 to 40 mol% inorganic cocatalyst, such as for example between CeO _2, about 2: 3 To about 3: 2. In another embodiment, the semiconductor material to a co-catalyst material, for example, the ratio of CeO ₂ is about 1: 1 [50 mole% to 50 mole%. In some embodiments, CeO ₂ is a sol. In some embodiments, the gas sensor element contains a physical mixture of p-type semiconductor such as n-type semiconductor and CeO2, such as gamma-phase WO _3. In some embodiments, the gas sensor element comprises a physical mixture of gamma phase WO ₃ and CeO ₂ from about 10: 1 to about 1: 2, from about 5: 1 to about 1: 1, from about 7: 3 to about 1: 1 or about 13: 8 weight ratio (WO ₃ : CeO ₂ ).

In some embodiments, n-type semiconductors, doped or undoped WO ₃ compounds, and / or cocatalysts, or composites thereof may be combustion synthesized. In some embodiments, the photocatalytic material is synthesized is about ^{9m 2 / g, 10m 2 /} g, 12m 2 / g, 15m 2 /g,17.5m 2 / g, and / or ^22m 2 / g greater than It may have a specific surface area. The value obtained for the specific surface area is obtained by methods known to those skilled in the art including, but not limited to, Brunauer-Emmett-Teller (N2-BET) adsorption methods. When the material is synthesized by combustion, for example, there is a resulting material having an elongated form of about 50-200 μm in length and a diameter of about 20 μm and a specific surface area of about 6-8 m ² / g (see Example 10, Table 5). , See FIG. 12A), for example, according to BET, was found to have an SSA of about 7 m ² / g. In some embodiments, without intending to be limited by theory, increasing the specific surface area of a combustion synthesized n-type semiconductor, eg, a compound of Formula 1, corresponds to an increase in sensor sensitivity. I found it.

  In some embodiments, increasing the SSA can result from reducing the size of the combustion synthesized particles. In some embodiments, increasing the SSA can result from modifying the elongated rod to make it a more spherical particle of combustion synthesized particles. In some embodiments, altering the morphology of the combustion synthesized particles can be by making the particles more spherical. In some embodiments, increasing the SSA can be by ball milling the combustion synthesized material. In some embodiments, increasing the SSA may be by sonicating the dispersion of combustion synthesized material and then selectively separating the reduced size sonicated material. .

In some embodiments, increasing the SSA can be by ball milling the combustion synthesized material. In some embodiments, increasing the SSA may result from wet milling the combustion synthesized material. In some embodiments, wet milling may include dispersing the desired material / precursor in a carrier solvent. In some embodiments, the carrier solvent may be a _C 1 -C ₅ alcohol. In some embodiments, the C ₁ -C ₅ alcohol can be isopropanol, methanol, and / or ethanol, or a mixture thereof. The amount of sample to be ball milled, the size of the mill ball, the length of the milling time, and the speed / rotation of the ball mill machine are considerations for the amount of ball milling sufficient to increase the SSA by a sufficient amount. is there. In some embodiments, the millball can be about 1 mm to about 10 mm in diameter, such as 3 mm and / or 5 mm in diameter. In some embodiments, the millball can include a plurality of millballs of at least first and second sizes, first and second millballs of different diameters. In some embodiments, the ratio of the first and second millballs is a ratio of about 1: 1 wt% of the amount of millballs of the first millball diameter to the amount of millballs of the second millball diameter, 2.5: 1. The ratio can range from 4: 1 ratio, 5: 1 ratio, 7.5: 1 ratio, and / or 10: 1 wt% ratio. In some embodiments, the first millball may have a smaller diameter than the second millball. For example, for ball milling, about 2.00 g of WO ₃ /0.05% B and 15.00 ml of methanol, 20 g of 3 mm mill balls, and 4 g of 5 mm mill balls can be used.

  Ball milling can reduce the diameter of polycrystalline n-type semiconductors. This can help to prepare a uniform and uniform coating of semiconductor on the sensor platform. In some embodiments, the polycrystalline n-type semiconductor or the polycrystalline physical mixture of the n-type semiconductor and the p-type semiconductor is about 0.01 μm to about 1 μm, about 0.1 μm to about 1 μm, or It may have a diameter or average diameter of about 0.2 μm to about 0.5 μm, or any diameter that is limited by or within the range of any of these values.

In some embodiments, the length of time for ball milling the material can be between about 0.5 hours to about 1 week, 1 hour to about 72 hours, about 12 hours to about 36 hours. In some embodiments, the length of time described above may be due to the size of the millball described above. In some embodiments, it is about 17 hours to ball mill about 2.00 g of WO ₃ /0.05% B, 15.00 ml of methanol, 20 g of 3 mm mill balls, and 4 g of 5 mm mill balls. obtain.

  In some embodiments, the ball mill processing machine may be a planetary ball mill. An example of a suitable ball mill may be the SFM-1 desktop planetary ball mill (MTI-Corp, Richmond, CA, USA). In some embodiments, the planetary ball mill may be set to rotate at about 500 rpm, 1000 rpm to about 2500 rpm, 5000 rpm, or 10,000 rpm, or any combination of the above rotational speeds. In some embodiments, the planetary ball mill can rotate at about 1500 rpm.

  In some embodiments, SSA may be increased by sonicating a dispersion of combustion synthesized material and then selectively separating the reduced size sonicated material. In some embodiments, sonicating can be by vibrating the sample at about 35 kHz. In some embodiments, sonicating can be from about 5 minutes to about 6 hours. A suitable sonicator may be a SYMPHONY ™ Ultrasonic Cleaner (VWR, model no. 97043-958). In some embodiments, sonicating at about 35 kHz can be about 60 minutes. In some embodiments, selectively separating the reduced size sonicated sample is immediately adjacent to the surface of the sonicated sample dispersion for drop deposition on the sensor substrate. This can be by separating an aliquot from the bottom.

  In some embodiments, the sensor may detect a test component. In some embodiments, the test component can be polar. In some embodiments, the test component is, for example, about 1.00D, about 1.25D, about 1.30D, about 1.40D, about 1.50D, about 1.60D, about 1.70D, about 1. It may have a dipole moment greater than .85D, about 1.90D, about 2.00D, about 2.25D, or about 2.50D. Exemplary materials and their dipole moments are listed in Table 3 below.

  In some embodiments, the analyte can be a gas. In some embodiments, the test component can be acetone, and in some embodiments, the test component can also be ethanol.

  In some embodiments, a method for making a sensor composition is described that includes creating an aqueous n-type semiconductor precursor solution, heating the solution in a preheated device, and the preheated device. Includes preheating to substantially close to the combustion temperature of the aqueous solution, subjecting the precursor solution to a combustion reaction, and annealing the combustion reaction product. In some embodiments, the equipment can be preheated to at least about 420 degrees Celsius.

  FIG. 1 illustrates an embodiment of a sensor element 10. In some embodiments, the sensor element 10 can include a first electrode 14 and a second electrode 18. In some embodiments, the sensor can include an n-type semiconductor material 16 disposed between the first and second electrodes. In some embodiments, the n-type semiconductor material can electrically connect the first and second electrodes. In some embodiments, the n-type semiconductor material can be disposed between the first and second electrodes and / or in physical contact with both.

  As shown in FIG. 1, the sensor element 10 may include a first electrode 14. In some embodiments, the first electrode can include one or more electrode fingers 14A, 14B, 14C, 14D, 14E disposed on a substrate, eg, an alumina support. In some embodiments, the sensor element 10 can also include a second electrode 18. In some embodiments, the second electrode 18 may also include one or more electrode fingers 18A, 18B, 18C, 18D, and 18E. In some embodiments, each electrode finger is meshed with each other. In some embodiments, the electrode fingers are close enough to allow the semiconductive material to close the electrical circuit across the gap. In some embodiments, the electrode fingers can be at least 2, at least 3, at least 4, or at least 5 interdigitated fingers. In some embodiments, there may be a distance between the first electrode 14 and the second electrode 18. In some embodiments, the distance between the electrodes can be between 0.01 mils to about 100 mils, between about 0.1 mils to about 25 mils, and / or between about 0.5 mils to about 10 mils, In embodiments, the electrodes of the device may include a plurality of interdigitated fingers, such as 14A-14E.

  In some embodiments, the sensor element includes a semiconductor material 16. In some embodiments, the semiconductor material is high enough to substantially cover the first and second electrodes, and in some embodiments, the height of the semiconductor material is from about 1 μm to about It can be between 10 μm, about 2 μm to about 7 μm, about 3 μm to about 5 μm, and / or any combination of the values described above. As shown in FIG. 2, in some embodiments, the semiconductor 16, eg, 16A, 16B, 16C, 16D, 16E, includes a first electrode, eg, electrode fingers 14A, 14B, and 14C, and a second Electrodes, such as second electrode fingers 18A and 18B, may be placed around and / or in electrical contact with them.

  As shown in FIG. 3, in some embodiments, the semiconductor can be placed over the electrodes. In some embodiments, the heater element 13 (eg, 13A, 13B) may be positioned proximate to the electrodes 14 and 18. Providing current through a heater element, such as a loop or circuit, can heat the substrate and / or the first and second electrodes to a desired temperature. In some embodiments, the sensor element includes at least a semiconductor 16 disposed between the electrodes. In some embodiments, the height of the semiconductor material 16 is higher than the height of the electrodes 14 and / or 18. In some embodiments, the semiconductor material includes primary particles having a maximum dimension that is less than the length of the gap between the electrode fingers. In some embodiments, the semiconductor 16 includes a semiconductor material having particles having a median diameter of about 0.2 μm to about 1.1 μm and / or about 0.3 μm to about 1.0 μm. In one embodiment, the median diameter can be between about 0.4 to about 0.8 μm and / or any combination of the described limitations. In some embodiments, the median diameter of the particles can be from about 0.4 μm to about 0.5 μm, such as about 0.50086 μm.

  The first and second electrodes can be formed from a conductive material. In some embodiments, the electrode can be gold (Au), platinum (Pt), palladium (Pd), and / or any mixture thereof.

  In some embodiments, the semiconductor 16 can include any of doped, supported, and / or physically mixed semiconductors.

  The temperature at which the sensor element functions can be affected by different semiconductor materials, dopants, supports, and / or cocatalysts. In some embodiments, the electrodes 14 and 18 are disposed on the substrate 12. In some embodiments, the heater element 13 is positioned proximate to the electrodes 14 and 18. In some embodiments, the n-type semiconductor composition combined with any dopant and / or cocatalyst can be formed into a slurry. The slurry can be drop coated on the electrode and substrate. In some embodiments, excess slurry can be separated from the acetone sensor element so that the remaining n-type semiconductor slurry fills the gap between the electrodes as in FIG.

  In some embodiments, the sensor element may detect the presence of the analyte gas within a range of temperatures. In some embodiments, the sensor element may detect the presence of the analyte gas between 0 ° C and 400 ° C. In some embodiments, the sensor element may detect the presence of the analyte gas at between about 0 ° C. and about 200 ° C., about 100 ° C. and about 300 ° C., or between about 200 ° C. and about 400 ° C. In some embodiments, the sensor element is about 0 ° C. and about 20 ° C., about 20 ° C. and about 40 ° C., about 40 ° C. and about 60 ° C., about 60 ° C. and about 80 ° C., about 80 ° C. and about 100 ° C., About 100 ° C and about 120 ° C, about 120 ° C and about 140 ° C, about 140 ° C and about 160 ° C, about 160 ° C and about 180 ° C, about 180 ° C and about 200 ° C, about 200 ° C and about 220 ° C, about 220 ° C And about 240 ° C, about 240 ° C and about 260 ° C, about 260 ° C and about 280 ° C, about 280 ° C and about 300 ° C, about 300 ° C and about 320 ° C, about 320 ° C and about 340 ° C, about 340 ° C and The presence of the analyte gas can be detected between about 360 ° C, about 360 ° C and about 380 ° C, or about 380 ° C to about 400 ° C, or limited by any of these values. Luke or is any temperature therebetween. In some embodiments, the sensor may detect the presence of the analyte gas at some or any combination of the temperatures described above. In some embodiments, the sensor element may detect the presence of the analyte gas at room temperature. In some embodiments, the analyte gas can be acetone, ethanol, and / or both acetone and ethanol.

In some embodiments, the polycrystalline n-type semiconductor device, such as boron-doped epsilon WO ₃ , is above about 150 ° C, such as about 150 ° C to about 400 ° C or about 190 ° C to about 360 ° C. It can operate at temperatures above about 190 ° C. In some embodiments, the polycrystalline n-type semiconductor device, such as boron-doped epsilon WO _3, is at a temperature greater than about 280 ° C or about 310 ° C, such as about 280 ° C or about 310 ° C to about 360 ° C. When activated, it can be more sensitive to isoprene than acetone or ethanol. In some embodiments, a polycrystalline n-type semiconductor device such as boron-doped epsilon WO ₃ isoprene when operated at a temperature below about 240 ° C., such as about 180 ° C. to about 240 ° C. Or it may be more sensitive to acetone than ethanol.

In some embodiments, the sensor element may detect the presence of the analyte gas in the presence of visible light. In some embodiments, the visible light has a peak wavelength between about 350 nm, about 375 nm, about 400 nm to about 500 nm, 550 nm, 600 nm, and / or 650 nm, or a range of any combination of the foregoing wavelengths. obtain. In some embodiments, the sensor element may detect the presence of the analyte gas in the presence of light having a wavelength of less than 650 nm, less than 600 nm, less than 550 nm, less than 500 nm, less than 450 nm, less than 400 nm. In some embodiments, the sensor element is a gas of a test component in the presence of an LED having a power of about 30-40 mW / cm ² that emits at the wavelength described above, eg, about 455 nm, eg, a blue LED (BLED). The presence of can be detected. In some embodiments, the sensor may detect the presence of the analyte gas at room temperature in the presence of visible light as described above. It is believed that the resistivity may decrease when exposed to acetone in higher temperature sensor operation. In some cases, room temperature operation of the sensor appeared to show an increase in resistivity change when exposed to acetone under BLED light.

In some embodiments, a polycrystalline n-type semiconductor material such as a gamma phase WO ₃ with a cocatalyst, for example CeO ₂ or TiO ₂ , is used when the polycrystalline n-type semiconductor material is visible light such as blue light, eg When exposed to light having a wavelength of about 450 nm to 495 nm, volatile organic compounds such as acetone, ethanol, or isoprene are about 10 ° C. to about 50 ° C., about 10 ° C. to about 40 ° C., about 20 ° C. to about Detection can be at low temperatures such as 30 ° C., about 25 ° C. to about 30 ° C., or about room temperature.

  FIG. 4A illustrates one embodiment of the sensor system 10. In some embodiments, the first electrode 14 and the second electrode 18 of the sensor element 10 are electrically connected to a resistivity monitor 22. It is believed that the presence of a test component in close proximity to the electrode and / or semiconductor, such as acetone, can increase the resistance of the circuit between electrodes 14 and 18 and provide a change in the measured resistivity of the circuit. In some embodiments, a measurable correlation can be achieved between the amount of analyte, such as acetone, present in close proximity to the electrode and the variation in resistance exerted by the circuit. In some embodiments, the change in resistivity may be at least about 152 megaohms per 100 parts per million (ppm) of the test component present during the sampling being tested. The reading is obtained by directly measuring the absolute resistance value and its change using a computer controlled multimeter.

  FIG. 4B illustrates another embodiment of a sensor system 10 for detecting the presence of a analyte gas, eg, acetone, in a volume of gas. The apparatus may include a chamber 5 for containing a large amount of gas to be evaluated and a sensor element 10 disposed therein. In some embodiments, the chamber 5 may include a gas inlet 11 that allows gas inflow 9. In some embodiments, the chamber 5 may include a gas outlet 13 that allows gas outflow. In some embodiments, the device may include a power source 20 and a measurement device 30 for analyzing data received from the acetone sensor element.

FIG. 7 illustrates a schematic diagram of an acetone sensor system for detecting the presence of acetone in the volumetric gas described in Example 11.

FIG. 7A illustrates another embodiment of a sensor system 100 for detecting the presence of the analyte gas. Instrument includes a chamber over for holding the gas sample, the sensor device 10 for analyzing gas samples, and air flow disturbance element 17 for influencing near the airflow sensor device 10. The instrument may also include a gas inlet 11 for introducing a gas sample into the chamber. In some embodiments, the gas inlet 11, the first airflow obstruction element 17, and the sensor device 10 are configured to substantially reduce the amount of gas sample that travels without collision from the gas inlet 11 to the sensor device 10. , Can be arranged coaxially. The sensor device can be a solid state sensor for detecting the presence of volatile organic compounds (VOC) in a gas sample. In some embodiments, the instrument 100 can include a gas outlet 13. In some embodiments, the gas outlet 13 may be arranged such that the gas sample flowing from the gas inlet 11 to the sensor device 10 must change the direction of flow before exiting the gas outlet 13. In some embodiments, as shown in FIG. 7A, the gas inlet 11, the first airflow obstruction element 17, and the sensor device 10 can be coaxial and are disposed in the gas outlet 13 and therein. A second air flow obstruction element 19 can be arranged on the wall of the chamber, oriented at a right angle (90 °) to the axis of the aforementioned component. The gas inlet 11 may be in fluid communication with the sensor device 10, the airflow obstruction element 17, and the gas outlet 13. The gas outlet 13 may be in fluid communication with the gas inlet 11, the sensor device 10, and the airflow obstruction element 17.

  Embodiments also encompass a method for manufacturing the described acetone sensor element. In some embodiments, the method includes creating an aqueous n-type semiconductor precursor solution and heating the solution in the preheated equipment, where the preheated equipment is preheated to substantially close to the combustion temperature of the aqueous solution. And a step of subjecting the precursor solution to a combustion reaction and a step of annealing the combustion reaction product.

Embodiments also include a method for identifying acetone in mammalian breath, exposing a mammalian breath sample to a sensor comprising a polycrystalline n-type semiconductor material of formula P _1-x B; (Where B is boron, 0.0001 <x ≦ 0.10, the semiconductor material has an absorption edge of 600 nm or less), and the presence of acetone is determined by measuring the change in resistivity of the sensor Including.

Embodiments also include a method for making a sensor element, comprising first and second spaced apart electrodes interdigitated with combustion synthesis of boron-doped epsilon or gamma phase WO ₃ semiconductor And providing a combustion synthesized boron doped epsilon or gamma phase semiconductor between the first and second spaced apart electrodes. In some embodiments, the method may include increasing the SSA of the combustion synthesized semiconductor material. In some embodiments, increasing SSA can be accomplished by ball milling the combustion synthesized semiconductor material. In some embodiments, SAA can be achieved by sonicating a dispersion of combustion synthesized material and then selectively separating the reduced size sonicated material. In some embodiments, boron-doped epsilon or gamma phase WO ₃ semiconductor can be ball milled in a time and / or manner sufficient to achieve the median size description described above. In some embodiments, the method further includes reducing the semiconductor diameter population to the aforementioned range, eg, a median size of about 0.4 to about 0.6 μm. In some embodiments, the foregoing ranges are achieved by ball milling boron-doped epsilon or gamma phase WO ₃ semiconductor for about 1 to about 72 hours, for example about 17 hours. In some embodiments, the aforementioned range is achieved by ball milling boron-doped epsilon or gamma phase WO ₃ semiconductor between about 500 rpm and about 5000 rpm, eg, about 1500 RPM. In some embodiments, the aforementioned ranges include ball milling boron-doped epsilon or gamma phase WO ₃ semiconductor between about 500 rpm to about 5000 rpm, between about 1500 RPM, between about 5 to about 25 hours, such as about 17 hours. Is achieved by doing In some embodiments, the method further comprises adding a first ball diameter population to the boron-doped epsilon or gamma phase WO ₃ semiconductor. In some embodiments, the balls used for ball milling can be Al ₂ O ₃ and / or ZrO ₂ . In some embodiments, the ZrO ₂ ball may include multiple diameter populations. In some embodiments, the plurality of diameter populations may include a first population of about 3 mm ZrO _{2 and} a second population of about 5 mm ZrO ₂ .

  It has been discovered that the embodiments described herein have improved operating environment parameters and / or sensitivity to acetone compared to other sensor embodiments. These advantages are further illustrated by the following examples, which are intended to illustrate embodiments of the present disclosure, but are not intended to limit the scope or basic principles in any way.

Example of sensor material development and characterization Preparation of boron-doped epsilon phase WO ₃ Ammonium metatungstate hydrate (5 g), boric acid (100 mg), carbohydrazide (fuel) (2 g), and ammonium nitrate (oxidant) (10 g) were deionized ( DI) dissolved in 50 ml of water. The aqueous solution was then placed in a muffle furnace preheated to about 420 ° C. and then heated for about 20 minutes or until material burning was substantially complete. After the sample material was combusted, the product was annealed in air at about 420 ° C. for an additional about 20 minutes. The object color of the powder appeared orange-yellow, and the boron-doped WO ₃ was confirmed by comparison with the powder XRD pattern (FIG. 5) by X-ray diffraction of standard epsilon WO ₃ (ICFF PDF card number 01-087- 2404). A scanning electron micrograph of the resulting material is shown in FIG. 12A.

Three 0.05 g samples of B-doped WO ₃ particles were analyzed by ICP-MS to identify the content of various elements. Each sample was mixed with 1 mL nitric acid and 3 mL hydrochloric acid and then heated at about 110 ° C. for about 1 hour. After cooling, a sufficient amount of internal standard solution (eg, according to B3 and / or B doped WO ₃ ) was added to dilute the solution of the dissolved sample into an approximately 100 g sample aliquot for ICP-MS analysis. Sample aliquots were then spiked with known concentrations of Sc and In. The common standard elements, blanks, and sample solutions were then introduced into an Agilent 7500 cx inductively coupled plasma mass spectrometer (ICP-MP). The concentration of approximately each element in the sample solution was quantitatively identified and shown in Table 3A below.

Examples 2-10
Examples 2-10 were made in a manner similar to Example 1. However, the amounts of boric acid (“B”), carbohydrazide (“C”), and / or ammonium nitrate (“D”) were varied as described in Table 4 below.

Examples 11-13
Example 11 Boron doped epsilon WO ₃ noble metal support 1 g of Example 1 made in the manner described above and 17.12 mg of [Pt (NH ₃ ) 4] (NO ₃ ) ₂ in 10 mL distilled water. And stirred at about 90 ° C. for about 2 hours in a 40 mL sealed vial reactor. The sealed vial is then cooled in room temperature tap water, filtered through a membrane filter (0.05 μm pore size), washed at least three times with DI water, and finally dried at about 110 ° C. overnight (about 15 hours), 1 wt% About 45 mg of epsilon phase WO ₃ loaded with Pt was obtained.

Examples 12, 13, and 14 were made in a manner similar to Example 11 (1% Pt-ε-WO ₃ ). However, in Example 12, 1 g of gamma phase WO ₃ (Sigma Aldrich, St. Louis, MO, USA) was used instead of epsilon phase WO ₃ (1% Pt-γ [gamma] -WO ₃ ), and in Example 13, boron ( B) 1 g of gamma WO ₃ without was used in place of 1% Pt-epsilon phase WO ₃ and in Example 14 a physical mixture of 13 g of gamma phase WO ₃ and 8 g of CeO ₂ was prepared. 1g was used instead of 1g of 1% Pt-epsilon phase WO _3.

Example 14
Example 14A. Ball milled slurry 2.00 g of WO ₃ /0.05% B and 15.00 ml of methanol prepared as described above in Example 1 are added to a high purity alumina jar for solvent based slurry preparation. The contents of the mill jar were then manually stirred until the mixture appeared liquid. Then, the 4g of ZrO ₂ mil material 20g and 5mm diameter ZrO ₂ mil material 3mm in diameter was added to an alumina jar, the mixture benchtop planetary ball mill in the mill jar (MTI Corporation, Richmond, CA) at room temperature for about 1500rpm by Milled for about 17 hours. The resulting mixture was then dried in air at about 110 ° C. for about 2 hours. A scanning electron micrograph of an embodiment of the resulting ball milled slurry is shown in FIG. 12B.

Example 14B
In another example, 2.00 g WO ₃ /0.19 wt% B made as described above was used in place of 2.00 g WO ₃ /0.05% B.

Example 14C. Particle Size Analysis Particle size distributions before and after ball milling were obtained with a Horiba LA-300 particle size distribution analyzer (Horiba Scientific, Edison, NJ, USA).

2 g of aqueous sodium pyrophosphate decahydrate (SPD) was dissolved in about ₂ L of reverse osmosis water (ROH ₂ O) to make an SPD solution (0.1 wt% sodium pyrophosphate decahydrate).

For cleaning, ₂ L of additional ROH ₂ O was circulated through Horiba's LA-300 sample chamber and sonicated for 1 minute (“De-bubble” on). Circulated and sonicated ROH ₂ O was drained from the sample chamber and the chamber was refilled with SPD solution (Horiba settings were circulation “8” and “De-bubble”). The machine was blank adjusted (settings are “Init.Alignment”, “Alignment”, “Blank”) and repeated to ensure that the total transmission percent (T%) of the blank was T% = 100%.

An initial amount of about xg of ball milled 0.19 wt% B doped WO ₃ (made as described in Example 12B [SE-1BM] above) is added in about 25 ml of SPD solution. Transfer and mix well (about 5 minutes). The SE-1BM mixture was loaded into the sample chamber until the T% dropped from about 75% to 80%. When such T% is reached, circulation “8”, 10 minutes sonication, “De-bubble” during 10 minutes sonication, and about 1.654 (R _powder / R _solvent = refractive of powder Ratio / solvent refractive index = WO ₃ / H ₂ O = 2.22 / 1.33 = 1.654) “RR Index” (solvent refractive index)) setting, particle size distribution Was obtained (see FIG. 13). The particle size distribution of the non-ball milled sample (SE-3) was prepared in the same manner as described above. However, the SE-3 material was used instead of the ball milled 0.13 wt% B doped WO ₃ (SE-1BM). The result is illustrated in FIG.

The particle diameter size reduction and / or transition is illustrated in FIG. The median diameter of WO ₃ /0.05% B particles without ball milling is about 13.7233 μm, while the median diameter of the above WO ₃ /0.05% B particles with ball milling is about 0.5086 μm. there were.

Example 15: Sensor Fabrication and Sensor Material Drop Coating Example 15A: No Ball Mill Treatment About 9 mg of platinum supported ε-phase tungsten oxide prepared above was mixed with isopropyl alcohol (IPA) (0.4 ml) for 60 minutes. Sonicated. About 10 10 μl aliquots of the dispersion are separated from just below the surface of the sonicated dispersion and then a sensor element having a surface temperature of about 120 ° C. (0.1 × 0.1 inch electrode, Al ₂ O ₃ substrate, 10 mil thickness, electrode material Au, electrode spacing 1 mil, finger width 4 mil, finger length 0.1 inch, 3 electrode pairs, P / N 614, Syncera Technologies, Colorado, USA) Dried between each additional drop. The drop-coated sensor (SE-1) was then baked at about 120 ° C. for about 60 minutes under a 300 W output power full spectrum xenon lamp.

  Drop-coated sensors 2 (SE-2), 3 (SE-3), 4 (SE-4), and 5 (SE-5) were assembled in the same manner as described above. However, the materials dispersed in IPA were as shown in Table 5 below.

An SEM photograph of ε-WO ₃ (SE-3) loaded with 1 wt% Pt is shown in FIG.

Example 15B: Sensor fabrication with ball milling Approximately 10 mg of the ball milled tungsten oxide prepared above was mixed with methanol (1.0 ml) and sonicated for 60 minutes. About seven 10 μl aliquots of the dispersion were applied to a sensor element having a surface temperature of about 120 ° C. (0.1 × 0.1 inch electrode, Al ₂ O ₃ substrate, 10 mil thickness, electrode material Au, electrode spacing 4 mil, finger width 4 mil, finger length 0.1 inch, 3 electrode pairs, P / N 614, Syncera Technologies) and dried between each additional drop. The drop-coated sensor (SE-1BM) was then baked at about 120 ° C. for about 60 minutes under a 300 W output power full spectrum xenon lamp.

Example 16: Evaluation of acetone sensor Sensor element 3 (SE-3) assembled as described in the above example is placed in a metal chamber having a volume of about 850 mL and the sensor electrode is placed on a multimeter (Tektronix DMM 4050, 6. Connected to 1/2 digit high-precision multimeter, Tektronix Inc., Beaverton, OR, USA), set to measure resistivity (ohms) at about 40mΩ, complete dark room under ambient atmospheric conditions Put it on. See Figure 7. The sensor electrode was then exposed to an operating temperature of about 350 ° C. Acetone-free air (compressed synthetic air [CAS132259-10-0], air gas LLC, San Marcos, CA, USA) having a relative humidity of about 90% is released into the container at about 1 ml / min for about 10 minutes, and The chamber was withdrawn at the same rate (to minimize chamber pressurization) and a resistivity baseline reading was recorded. Then 1 ppm acetone / air gas (A-030-1090-100 PNA compressed 1 ppm acetone / synthetic air, Mesa Specialty Gases & Equipment, Long Beach, CA, USA) in the container for various times, eg 60 sec, about 30 sec, about 10 sec. For about 5 seconds, and the resistivity of the sensor element was recorded. The gas environment in the chamber was determined by a gas chromatograph (Agilent gas chromatograph model 7890A, Agilent mass spectrophotometer model 240) attached to the mass spectrophotometer. The result is shown in FIG. FIG. 9 shows that when the sensor operating temperature was about 350 ° C., the sensor element exhibited sensitivity to about 1 ppm of acetone in the air.

Example 17: Evaluation of acetone sensor Sensor elements 5 and 4 were assembled as described in Example 16 above and tested as described immediately above. However, the sensor was maintained at about room temperature, the sensor was exposed to an array of light emitting diodes emitting blue light, and the BLED emitted at a wavelength of about 455 nm and about 35-40 mW / cm ² . The results are provided in Table 6.

  FIG. 8 shows that the sensor element was sensitive to about 100 ppm of acetone in the air when the sensor operating temperature was room temperature.

Example 18: Evaluation of acetone sensor SE-1BM was assembled as in the above example and tested in a manner similar to that of Figure 7 above. In this example, instead of the 850 ml metal chamber described immediately above, it is described in US Provisional Application 62 / 064,680, Oct. 16, 2014, all of which it discloses is incorporated herein by reference. The T-shaped inspection chamber (TC-1) is used. TC-1 was constructed from a 7.62 cm long (polycarbonate) tube with an inner diameter of 2.6 cm. The inspection chamber had a gas outlet with an inner diameter of 1 cm, formed a right-angle t-shaped junction with the instrument chamber, and the center of the gas outlet was aligned with the sensor device. The center of the gas outlet and the sensor device (example 1 sensor assembled on Syntek 614 chip with heater circuit) was provided 3.81 cm from the end of the instrument. The instrument chamber was sealed just below the gas outlet hole at the bottom edge approximately 4.3 cm from the top. The instrument had a gas inlet with a circumference of 1 cm in the center of the top end of the instrument. The instrument also had a wire mesh screen that acted as an airflow reducing element filling the gas outlet tube. The airflow reducing element is a high corrosion resistance type 316 stainless steel wire cloth disc, having a wire diameter of 0.01 inches, a mesh size of 40 × 40, an opening size of 0.015 inches, and an open area of about 36%. (McMaster-Carr-2930T43, McMaster-Carr, Los Angeles, CA, USA). FIG. 7A shows the above-described inspection chamber. The airflow obstructing element was suspended in the instrument by four mooring wires and the screen was fixed. The airflow obstructing element was 1.5 cm in diameter, was provided 1 cm above the surface of the sensor device in the instrument chamber, and was concentric with the test chamber tube. The wire mesh screen is a high corrosion resistant 316 stainless steel wire cloth disc (McMaster-Carr-2930T63, McMaster-Carr), 0.0045 inch wire diameter, 100 × 100 mesh size, 0.0055 inch mesh size And created an open area of about 30%.

The sensor element 3 (according to the heater circuit board Syncera-P / N614) assembled as in the above example is placed in the T-shaped chamber described above, and the sensor electrode is a multimeter (Tektronix DMM 4050, 6. Connected to a ½ digit high precision multimeter, Tektronix Inc.), the resistivity (ohms) was set to measure under ambient atmospheric conditions at about 40 mΩ. See Figure 7. The sensor electrode heater circuit (614) was then exposed to 5.6 volts with a drive current of about 0.156 amp using a Gw.Instek PST-3202 power supply, and the sensor body was heated for about 72 hours. During the measurement, the sensor body was heated to about 300 ° C. at a voltage of 5.2 volts and 0.153 amp. Acetone-free air (compressed synthetic air [CAS132259-10-0], air gas LLC, San Marcos, CA, USA) having a relative humidity of about 90% is released into the container at about 1 ml / min for about 5 minutes, and The chamber was withdrawn at the same rate (to minimize chamber pressurization) and a resistivity baseline reading was recorded. A pulse of about 10 ppm acetone / air gas (A-030-1090-100 PNA compressed 1 ppm acetone / synthetic air, Mesa Specialty Gases & Equipment) is then released into the container at about 1 liter / minute for about 5 minutes, and the resistance of the sensor element The rate was recorded. Acetone-free / synthetic air pulse, followed by 1 ppm sample acetone pulse, was repeated twice. Acetone-free pulses were then applied to the sensor system, followed by 15 ml, 2.5 ml, 1 ml / min acetone sample pulses with each intervening acetone-free spacing pulse. The results are provided in FIG. The sensor response as a function of acetone concentration derived from FIG. 10 is shown in FIG.

Example 18A
The sensor element 1 (as per the heater circuit board Syncera-P / N614) assembled as described above is placed in the T-shaped chamber described above, and the sensor is a multimeter (Tektronix DMM4050, 6.1 / 2 digit). Connected to a high-precision multimeter, Tektronix Inc., Beaverton, OR, USA), the resistivity (ohms) was set to measure in ambient atmosphere and dark conditions at about 40 kΩ. The sensor was heated to about 195 ° C. by applying a voltage of 3.8 volts and a current of 0.137 amp to the platinum resistance heater. Acetone-free air (compressed synthetic air [CAS132259-10-0], air gas LLC, San Marcos, CA, USA) having a relative humidity higher than 90% is placed in a T-shaped tube container at about 1.5 l / min. , The baseline of the resistivity of the sensor (the apparent plateau in the resistance profile is about 42,000 ohms corresponding to the interval of 3,050 to about 3,100, the first of the resistivity profiles of FIG. 1) was established for about 300 seconds. A 15.1 ppm acetone / synthetic air mixture was then passed through the system at about 110 mL / min simultaneously with an air flow of 1.5 L / min and the resistivity change was monitored at a temperature of 195 ° C. for about 150 seconds. The acetone flow was then closed to re-establish the sensor resistivity baseline, and the acetone-free synthetic air was flushed for about 300 seconds (at about intervals 3,150 to about 3,250, about Reversion of resistivity from 15,000 ohms to about 39,000 ohms). Then, ethanol gas (99.4 ppm acetone / synthetic air mixture, 10 mL / min flow rate) is mixed with the aforementioned 1.5 L / min synthetic air flow to allow the resistivity change to occur at a temperature of 195 ° C. for about 150 seconds. Observed. The ethanol flow was closed again to re-establish the sensor resistivity baseline, and the ethanol-free synthetic air was flushed for about 300 seconds (about 35, 3-5, as seen in FIG. Resistivity from 000 ohms to about 39,000 ohms). Then, isoprene gas (100.9 ppm isoprene / synthetic air mixture, 10 mL / min flow rate) is mixed with isoprene-free synthetic air (1.5 L / min) and the change in resistivity is observed at a temperature of 195 ° C. for about 150 seconds. did. The isoprene flow was then closed again to stabilize the sensor's resistivity baseline (recovery of resistivity from about 15,000 ohms to about 37,500 at about interval 3,500).

Examples 19-27
Examples 19 to 27 were tested in a manner similar to that described in Example 18A above. However, the sensor device was heated to various temperatures by applying various voltages and currents as shown in Table 7 below.

FIG. 14 shows that the sensor element exhibits a relatively constant sensitivity for ethanol and isoprene, while for acetone, the higher sensitivity (higher than 300 ° C., for example, at 300 ° C. or higher). It shows that high R _air / R _gas was exhibited.

Embodiments The following embodiments are contemplated.
Embodiment 1. FIG. A first electrode and a second electrode separated by a gap of about 1 to about 10 mils;
A gas sensor element comprising: a polycrystalline n-type semiconductor material in physical contact with both the first electrode and the second electrode.
Embodiment 2. FIG. The polycrystalline n-type semiconductor is represented by the formula P _1-x B, where P is an n-type semiconductor material, B is boron, x is greater than about 0.0001 and greater than about 0.10. The gas sensor of any of the embodiments herein, such as Embodiment 1.
Embodiment 3. FIG. 3. A gas sensor according to any suitable embodiment herein, such as embodiment 1 or 2, wherein the semiconductor material has an absorption edge of 600 nm or less.
Embodiment 4 FIG. The polycrystalline n-type semiconductor material comprises a epsilon phase WO _3, embodiments 1, 2 or 3 or of the gas sensor element of appropriate embodiments herein, such as,.
Embodiment 5. FIG. The boron to the epsilon phase WO ₃ is doped, the gas sensor element of one of appropriate embodiments herein, such as the fourth embodiment.
Embodiment 6. FIG. 6. The gas sensor element of any appropriate embodiments herein, such as embodiment 5, wherein the boron is present from about 0.001% to about 1% based on the weight of the polycrystalline n-type semiconductor.
Embodiment 7. FIG. 7. A gas sensor element according to any of the embodiments herein, such as embodiments 1, 2, 3, 4, 5, or 6, wherein the polycrystalline n-type semiconductor material is combustion synthesized.
Embodiment 8. FIG. Embodiments of any of the embodiments herein, such as embodiments 1, 2, 3, 4, 5, 6, or 7, wherein the polycrystalline n-type semiconductor is at a temperature of about 190 ° C. to about 360 ° C. Gas sensor element.
Embodiment 9. FIG. The gas sensor element of any suitable embodiment herein, such as embodiments 1, 2, 3, 4, 5, 6, 7, or 8, wherein said polycrystalline n-type semiconductor material comprises gamma phase WO ₃ .
Embodiment 10 FIG. The gas sensor element of any suitable embodiment herein, such as embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, further comprising a cocatalyst.
Embodiment 11. FIG. The gas sensor element of any suitable embodiment herein, such as embodiment 10, wherein the cocatalyst is a noble metal.
Embodiment 12 FIG. 13. The gas sensor element of any appropriate embodiment herein, such as embodiment 12, wherein the noble metal is palladium, gold, platinum, or iridium.
Embodiment 13. FIG. The gas sensor element of any suitable embodiment herein, such as embodiment 10, wherein the cocatalyst is CeO ₂ or TiO ₂ .
Embodiment 14 FIG. It said co-catalyst is CeO _2, the gas sensor element of one of appropriate embodiments herein, such embodiments 13.
Embodiment 15. FIG. The present specification, such as embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the polycrystalline n-type semiconductor material is exposed to blue light. A gas sensor element according to any suitable embodiment of the document.
Embodiment 16. FIG. Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 wherein the polycrystalline n-type semiconductor material is at a temperature of about 10 ° C. to about 40 ° C. Or the gas sensor element of any suitable embodiment herein, such as 15.
Embodiment 17. FIG. Embodiments 10, 11, 12, 13, 14, 15, wherein the ratio of the semiconductor material to the cocatalyst is about 60-40% of the cocatalyst with respect to the semiconductor material of about 40-60 mol%. Or a gas sensor element of any suitable embodiment herein, such as 16.
Embodiment 18. FIG. 18. A gas sensor element according to any suitable embodiment herein, such as embodiment 10, 15, 16, or 17, wherein the cocatalyst is a transition metal oxide (p-type).
Embodiment 19. FIG. The gas sensor element of any suitable embodiment of the present specification, such as embodiment 18, wherein the transition metal oxide is Co, Mn, Ni, or Cu oxide (p-type).
Embodiment 20. FIG. Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 in which the polycrystalline n-type semiconductor material is ball milled , 18, or 19 of any suitable embodiment of the gas sensor element herein.
Embodiment 21. FIG. A method for identifying acetone in a subject's breath, comprising: Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, Exposing the mammalian breath sample to a gas sensor comprising a gas sensor element of any appropriate embodiment herein, such as 17, 18, 19, or 20, wherein the presence of acetone is due to a change in sensor resistivity. The method to be detected.
Embodiment 22. FIG. The method of any suitable embodiment herein, such as embodiment 21, wherein the gas sensor operates at about 10 ° C. to about 50 ° C. and the gas sensor element is exposed to blue light.
Embodiment 23. FIG. The method of any suitable embodiment herein, such as embodiment 21, wherein the operating temperature of the gas sensor is from about 190 ° C to about 360 ° C.
Embodiment 24. FIG. The method of any suitable embodiment herein, such as embodiment 21 or 23, wherein the sensor is not exposed to blue light.
Embodiment 25. FIG. The method of any suitable embodiment herein, such as embodiment 23 or 24, wherein the gas sensor is operated at about 280 ° C. to about 360 ° C. and the gas sensor is more sensitive to isoprene than acetone.
Embodiment 26. FIG. The method of any suitable embodiment herein, such as embodiment 21 or 23, wherein the gas sensor is operated at about 180 ° C. to about 240 ° C. and the gas sensor is more sensitive to acetone than isoprene.
Embodiment 27. FIG. A method for making a sensor element, comprising: combusting and synthesizing boron-doped epsilon or gamma phase WO ₃ semiconductor; and a sensor element having first and second spaced apart electrodes interdigitated. And placing the combustion synthesized boron doped epsilon or gamma phase semiconductor between the first and second spaced apart electrodes.
Embodiment 28. FIG. Further, the boron-doped epsilon or gamma-phase WO ₃ semiconductor is ball milled for about 5 to about 25 hours, so that the specific surface area of the synthesized boron-doped epsilon or gamma-phase semiconductor is 10 m ² / g. The method of any suitable embodiment herein, such as embodiment 27, comprising increasing to greater than.
Embodiment 29. FIG. The Brunauer boron doped epsilon or gamma phase WO ₃ semiconductors - Emmett - Teller to increase (BET) is, epsilon or gamma phase WO ₃ semiconductor doped with the boron from about 1 hour to about 72 hours The method of any suitable embodiment herein, such as embodiment 27 or 28, comprising inter-ball milling.
Embodiment 30. FIG. Increasing the BET of the boron doped epsilon or gamma phase WO ₃ semiconductor prior to placement between the first and second electrodes, the boron doped epsilon or gamma phase WO ₃ 30. A method according to any suitable embodiment herein, such as embodiments 27, 28, or 29, comprising sonicating a semiconductor.
Embodiment 31. FIG. 32. A method according to any of the embodiments herein, further comprising adding a metal oxide to said boron-doped epsilon or gamma phase WO ₃ semiconductor.

  Unless otherwise indicated, all numbers representing the amount of ingredients, characteristics such as molecular weight, reaction conditions, etc. used in the specification and claims are in all cases modified by the term “about”. Should be understood. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained. At least not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, but each numerical parameter is at least in light of the number of significant digits reported and by applying normal rounding techniques Should be interpreted.

  The terms “a”, “an”, “the”, and similar designations used in the context of describing embodiments herein (particularly in the context of the following claims) are referred to herein differently. Unless otherwise indicated by context or explicitly denied by context, should be interpreted to cover both the singular and plural. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Use of any and all examples or exemplary language (eg, “such as”) provided herein is intended merely to better describe the disclosed embodiments, No limitation is imposed on the scope of such claims. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the disclosed embodiments.

  Alternative elements or groups of embodiments disclosed herein are not to be construed as limitations. Each group member may be referenced and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that for convenience and / or patentability, one or more members of a group may be included or deleted in a group. When any such inclusion or deletion occurs, this specification contains the modified group and is therefore considered to meet the description requirements of all Markush groups used in the appended claims.

  Certain embodiments are described herein, including the best mode known to the inventors for carrying out the spirit of the disclosure. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor anticipates that those skilled in the art will use such variations as appropriate, and that the inventor implements the disclosed embodiments differently than those specifically described herein. I intend to. Accordingly, the claims encompass all modifications and equivalents of the subject matter recited in the claims permitted by applicable law. Moreover, any combination of the elements described above is contemplated in all possible variations thereof, unless otherwise indicated herein or expressly denied by context.

  In conclusion, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the claims. Other modifications that may be used are within the scope of the claims. Thus, by way of example and not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the claims are not limited to the precise embodiments shown and described.

Claims (17)

A first electrode and a second electrode which are spaced apart by formic cap,
A polycrystalline n-type semiconductor material comprising epsilon phase WO ₃ doped with boron or gamma phase WO ₃ mixed with CeO ₂ or TiO ₂ ,
A gas sensor element in which the polycrystalline n-type semiconductor material is in physical contact with both the first electrode and the second electrode. The gas sensor element of claim 1, wherein the gap is from 0.000254 mm to about 2.54 mm. The gas sensor element of claim 1, wherein the boron is present from about 0.001% to about 1% based on the weight of the polycrystalline n-type semiconductor material .   The gas sensor element according to claim 1, wherein the polycrystalline n-type semiconductor material is synthesized by combustion. The gas sensor element of claim 1, wherein the polycrystalline n-type semiconductor material comprises an epsilon phase WO ₃ doped with boron , and the gas sensor element operates at a temperature of about 190 ° C to about 360 ° C.   The gas sensor element according to claim 1, further comprising a noble metal mixed with the polycrystalline n-type semiconductor material. The gas sensor element according to claim 6 , wherein the noble metal is palladium, gold, platinum, or iridium. The gas sensor element according to claim 1, wherein the gamma phase WO ₃ is mixed with CeO ₂ . The gas sensor according to claim 1, wherein the polycrystalline n-type semiconductor material includes gamma phase WO ₃ mixed with CeO ₂ or TiO _2, and the gas sensor element operates at a temperature of about 10 ° C to about 40 ° C. element. Wherein a gamma phase WO ₃ and the CeO ₂ or the CeO ₂ or TiO ₂ of about 60 to 40% relative to the gamma phase WO ₃ ratio of about 40 to 60 mole% of TiO _2, in claim 1 The gas sensor element described.   The gas sensor element according to claim 1, wherein the polycrystalline n-type semiconductor material is ball milled. A method for identifying acetone in a subject's breath, comprising:
Exposing a mammalian breath sample to a gas sensor comprising the gas sensor element of claim 1,
A method in which the presence of acetone is detected by a change in resistivity of the sensor.   The method of claim 12, wherein the gas sensor operates at about 10 ° C. to about 50 ° C. and the gas sensor element is exposed to blue light.   The method of claim 12, wherein the operating temperature of the gas sensor is from about 190 ° C. to about 360 ° C.   The method of claim 14, wherein the sensor is not exposed to blue light.   The method of claim 14, wherein the gas sensor is operated at about 280 ° C. to about 360 ° C. and the gas sensor is more sensitive to isoprene than acetone.   The method of claim 12, wherein the gas sensor is operated at about 180 ° C. to about 240 ° C. and the gas sensor is more sensitive to acetone than isoprene.

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